US7524999B2 - Process for the production of 1,1,1,3,3,3-hexafluoropropane - Google Patents
Process for the production of 1,1,1,3,3,3-hexafluoropropane Download PDFInfo
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- US7524999B2 US7524999B2 US11/792,644 US79264405A US7524999B2 US 7524999 B2 US7524999 B2 US 7524999B2 US 79264405 A US79264405 A US 79264405A US 7524999 B2 US7524999 B2 US 7524999B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
Definitions
- the present invention relates to the synthesis of 1,1,1,3,3,3-hexafluoropropane.
- This invention provides a process for the preparation of 1,1,1,3,3,3-hexafluoropropane.
- the process comprises (a) contacting at least one halopropane of the formula CF 3 CH 2 CH y X 3 ⁇ y (where each X is independently selected from the group consisting of F, Cl and Br, and y is 3, 2, or 1) with chlorine (Cl 2 ) in the presence of light or a free radical initiator to produce a mixture comprising CF 3 CH 2 CCl y X 3-y ; (b) contacting the CF 3 CH 2 CCl y X 3 ⁇ y produced in step (a) with HF, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CF 3 CH 2 CF 3 ; and (c) recovering CF 3 CH 2 CF 3 from the mixture produced in step (b).
- This invention provides a process for the preparation of 1,1,1,3,3,3-hexafluoropropane (CF 3 CH 2 CF 3 , HFC-236fa) from readily available starting materials.
- step (a) of the process of this invention one or more halopropane compounds CF 3 CH 2 CH y X 3-y , where each X is independently F, Cl, or Br, and y is 3, 2, or 1, are contacted with chlorine (Cl 2 ) in the presence of an initiator.
- the reaction of halopropane starting material(s) with chlorine is carried out in a reaction zone operated to provide substantial substitution of chlorine for the end-carbon hydrogens of the halopropane starting material(s) without substantial replacement of hydrogens on the middle carbon.
- at least 90%, and preferably greater than 95%, of the hydrogens of the CF 3 CH 2 CH y X 3 ⁇ y starting material replaced during step (a) are end carbon hydrogens.
- Free radical initiators such as peroxides or azo compounds may be employed.
- chlorine radicals are generated by the action of light on Cl 2 (i.e., photochlorination is preferably used).
- Suitable halopropane starting materials for step (a) include CF 3 CH 2 CHF 2 (HFC-245fa), CF 3 CH 2 CHClF (HCFC-244fa), CF 3 CH 2 CHCl 2 (HCFC-243fa), CF 3 CH 2 CH 2 Cl (HCFC-253fb), CF 3 CH 2 CH 2 Br (HCFC-253fbB), CF 3 CH 2 CH 2 F (HFC-254fb), and CF 3 CH 2 CH 3 (HFC-263fb). Due to their availability, CF 3 CH 2 CHF 2 (HFC-245fa), CF 3 CH 2 CH 2 Cl (HCFC-253fb), and CF 3 CH 2 CH 3 (HFC-263fb) are generally preferred.
- 1,1,1,3,3-Pentafluoropropane may be prepared by fluorination of HCC-240fa as described in U.S. Pat. No. 6,291,730.
- HCFC-253fb may be prepared by fluorination of 1,1,1,3-tetrachloropropane as disclosed in U.S. Pat. No. 4,078,007.
- HFC-263fb may be prepared by hydrogenation of 3,3,3-trifluoropropene as disclosed by Haszeldine in Journal of the Chemical Society, 1952, page 2510.
- the photochlorination of the halopropane starting materials of the formula CF 3 CH 2 CH y X 3 ⁇ y may be carried out in either the liquid or the vapor phase.
- initial contact of the starting materials with Cl 2 may be a continuous process in which one or more starting materials are vaporized (optionally in the presence of an inert carrier gas, such as nitrogen, argon, or helium) and contacted with chlorine vapor in a reaction zone.
- an inert carrier gas such as nitrogen, argon, or helium
- a suitable photochlorination reaction zone is one in which light having a wavelength of from about 250 nm to about 400 nm can irradiate the reaction components for a time sufficient to convert at least a portion of the halopropane starting materials to CF 3 CH 2 CCl y X 3-y .
- the source of light may be any one of a number of arc or filament lamps known in the art.
- Light having the desired wavelength may introduced into the reaction zone by a number of means.
- the light may enter the reaction zone through a lamp well or window fabricated from a material suitably transparent to light having a wavelength of from about 250 nm to about 400 nm.
- the walls of the reaction zone may be fabricated from such a material so that at least a portion of the light used for the photochlorination can be transmitted through the walls.
- suitable materials include quartz, glass, or fluoropolymers such as poly(tetrafluoroethylene) (e.g., Teflon® fluoropolymer), copolymers of perfluoro(alkyl vinyl ethers) (e.g., polyfluoroalkoxy resins such as Teflon® PFA fluoropolymer), and functionalized copolymers of terminally functionalized perfluoro(alkyl vinyl ethers) (e.g., perfluorosulfonic acid resins such as Nafion® fluoropolymer).
- poly(tetrafluoroethylene) e.g., Teflon® fluoropolymer
- copolymers of perfluoro(alkyl vinyl ethers) e.g., polyfluoroalkoxy resins
- chlorination step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from poly(tetrafluoroethylene), a copolymer of perfluoro(alkyl vinyl ether), or a functionalized copolymer of a terminally functionalized perfluoro(alkyl vinyl ether), and light is transmitted through said polymeric portion.
- the portion of the reactor wall fabricated from such polymeric materials may be limited to a fraction of the reactor wall (e.g., a window of the polymeric material positioned in a reactor principally fabricated from another material) or may constitute all or essentially all of the reactor wall (e.g., a tube reactor fabricated from the polymeric material).
- the process of the invention may be carried out in the liquid phase by feeding Cl 2 to a reactor containing the halopropane starting materials.
- Suitable liquid phase reactors include vessels fabricated from glass in which an external lamp is directed toward the reactor and metal or glass-lined metal reactors having one or more wells or windows for introducing light having a suitable wavelength.
- metal or glass-lined metal reactors having one or more wells or windows for introducing light having a suitable wavelength.
- fluoropolymer-lined metal reactors having one or more wells or windows for introducing light having a suitable wavelength.
- the reactor is provided with a condenser or other means of keeping the halopropane starting materials being irradiated to be in the liquid state in the reactor while permitting the hydrogen chloride (HCl) released during the chlorination to escape the reactor.
- HCl hydrogen chloride
- solvents suitable for step (a) include carbon tetrachloride, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1,1,2-trichlorotrifluoroethane, benzene, chlorobenzene, dichlorobenzene, fluorobenzene, and difluorobenzene.
- Suitable temperatures for the photochlorination of the halopropane starting materials of the formula CF 3 CH 2 CH y X 3 ⁇ y are within the range of from about ⁇ 20° C. to about 60° C. Preferred temperatures are typically within the range of from about 0° C. to about 40° C.
- step (a) in a liquid phase process is not critical so long as the liquid phase is maintained. Unless controlled by means of a suitable pressure-regulating device, the pressure of the system increases as hydrogen chloride is formed during step (a) by replacement of hydrogen substituents in the starting material by chlorine substituents. In a continuous or semi-batch process it is possible to set the pressure of the reactor in such a way that the HCl produced in the reaction is vented from the reactor (optionally through a packed column or condenser). Typical reactor pressures are from about 14.7 psig (101.3 kPa) to about 50 psig (344.6 kPa).
- the amount of chlorine (Cl 2 ) fed to the reactor is based on the value of y in CF 3 CH 2 CH y X 3-y .
- the ratio of Cl 2 to halopropane starting material is typically the stoichiometric amount required to substitute the hydrogen in the CH y X 3 ⁇ y Y group with a chlorine atom.
- y 3
- the molar ratio of Cl 2 to CF 3 CH 2 CH y X 3 ⁇ y is preferably about 3:1
- the molar ratio of Cl 2 to CF 3 CH 2 CH y X 3 ⁇ y is preferably about 2:1
- when y is 1, the molar ratio of Cl 2 to CF 3 CH 2 CH y X 3 ⁇ y is preferably about 1:1.
- a slight excess of chlorine over the stoichiometric amount may be desirable to facilitate conversion, but feeding a large excess chlorine to the reactor can result in a higher degree of halogenation in the products than is desirable.
- Examples of compounds that can be produced in step (a), particularly by photochlorination include CF 3 CH 2 CCl 3 (HCFC-233fb, produced from CF 3 CH 2 CH y X 3 ⁇ y starting material where y is 3, 2, or 1 and X is Cl), CF 3 CH 2 CBrCl 2 (HCFC-233fbB, produced from CF 3 CH 2 CH y X 3 ⁇ y starting material where y is 2 and X is Br), CF 3 CH 2 CCl 2 F (HCFC-234fb, produced from CF 3 CH 2 CH y X 3 ⁇ y starting material where y is 2 and X is F, or where y is 1, one X is Cl and the other X is F), and CF 3 CH 2 CClF 2 (HCFC-235fa, produced from CF 3 CH 2 CH y X 3 ⁇ y starting material where y is 1 and X is F).
- Under-chlorinated halopropane by-products that may be formed include compounds in which the value of y in CF 3 CH 2 CH y X 3 ⁇ y has been reduced from 3 to 2, from 3 to 1, or from 2 to 1.
- the effluent from step (a) may be subjected to one or more purification steps where the desired product, CF 3 CH 2 CCl y X 3 ⁇ y , is separated from HCl, under-chlorinated halopropane by-products, unreacted halopropane starting materials, and over-chlorinated halopropane by-products by distillation.
- unreacted halopropane starting materials and under-chlorinated halopropane by-products may be recovered and returned to step (a).
- step (b) of the process of the invention the CF 3 CH 2 CCl y X 3 ⁇ y produced in step (a) is contacted with HF, optionally in the presence of a fluorination catalyst, to produce a mixture comprising CF 3 CH 2 CF 3 .
- Step (b) of the process of the invention may take place in either liquid or the vapor phase.
- step (b) the reactor effluent from step (a) or the separated CF 3 CH 2 CCl y X 3 ⁇ y produced in step (a), is contacted with anhydrous hydrogen fluoride (HF) to form a mixture of fluorinated compounds.
- HF hydrous hydrogen fluoride
- the contacting of CF 3 CH 2 CCl y X 3 ⁇ y and HF may be conducted in the liquid phase in one of several ways.
- the process of the invention may be conducted in batch, semi-continuous, or continuous modes. In the batch mode, the CF 3 CH 2 CCl y X 3 ⁇ y step (b) starting material and hydrogen fluoride are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.
- liquid step (b) starting material of the formula CF 3 CH 2 CCl y X 3 ⁇ y is fed to a reactor containing liquid HF, or a liquid mixture of HF and fluorinated compounds formed by reacting HF with CF 3 CH 2 CCl y X 3 ⁇ y starting material, held at the desired reaction temperature.
- liquid HF may be fed to a reactor containing CF 3 CH 2 CCl y X 3 ⁇ y starting material, or a mixture of CF 3 CH 2 CCl y X 3 ⁇ y starting material and a mixture of fluorinated compounds formed by reacting HF with the CF 3 CH 2 CCl y X 3 ⁇ y starting material.
- both HF and CF 3 CH 2 CCl y X 3 ⁇ y starting material may be fed concurrently as liquids in the desired stoichiometric ratio to a reactor containing a mixture of HF and fluorinated compounds formed by reacting HF with CF 3 CH 2 CCl y X 3-y .
- the CF 3 CH 2 CCl y X 3 ⁇ y starting materials are preferably reacted with HF in the presence of fluorination catalysts selected from the halides, oxides, or oxyhalides of one or more metal compounds.
- Said metals may be selected from the group consisting of boron, aluminum, tin, titanium, vanadium, iron, zinc, arsenic, antimony, molybdenum, tungsten, niobium, and tantalum, and mixtures thereof.
- Said halides, oxides, or oxyhalides of one or more metal compounds may optionally be supported on carbon.
- fluorination catalyst compositions selected from the group consisting of AlF 3 , BF 3 , FeCl 3-a F a (where a is 0 to 3), FeZ 3 (where Z is halogen) supported on carbon, SbCl 3-a F a , AsF 3 , MCl 5-b F b (where b is 0 to 5 and M is Sb, Nb, Ta, or Mo), and M′Cl 4-c F c (where c is 0 to 4, and M′ is Sn, Ti, Zr, or Hf).
- Preferred fluorination catalyst compositions for the liquid phase embodiment of step (b) are those containing metal halides selected from the group antimony, tin, niobium, and tantalum.
- fluorination catalyst compositions useful for liquid phase step (b) embodiments include halides, fluorosulfonates or triflates of antimony, molybdenum, niobium, tantalum, tin or titanium as disclosed in U.S. Pat. No. 5,773,637.
- the temperature of the liquid phase embodiment of step (b) can be in the range of 50° C. to 175° C., preferably, 60° C. to 150° C.
- the pressure is selected so that the reaction medium is maintained in the liquid state.
- the pressure of the system increases as hydrogen chloride or hydrogen bromide are formed by replacement of chlorine or bromine substituents for fluorine subsituents in the CF 3 CH 2 CCl y X 3 ⁇ y starting materials and as the volatility of the organic components increases due to the formation of CF 3 CH 2 CF 3 .
- Typical reaction pressures are from about 20 psig (137.8 kPa) to about 1000 psig (6891 kPa).
- the molar ratio of HF to CF 3 CH 2 CCl y X 3 ⁇ y starting materials employed in the liquid phase embodiment of step (b) is typically from about 1:1 to about 100:1, preferably from about 3:1 to about 50:1 and most preferably from about 3:1 to about 30:1.
- reaction of HF with CF 3 CH 2 CCl y X 3 ⁇ y can also be carried out in the vapor phase (e.g., in a heated tubular reactor).
- a number of reactor configurations are possible, including horizontal or vertical orientation of the reactor and different modes of contacting the starting halopropanes with HF.
- the HF is substantially anhydrous.
- the step (b) starting material(s) may be fed to a reactor containing a fluorination catalyst.
- the halopropane starting material(s) may be initially vaporized and the vaporized starting materials and HF may be directly fed to a reaction zone containing a fluorination catalyst as gas(es).
- the step (b) halopropane starting material(s) may be contacted with HF in a pre-reactor.
- the pre-reactor may be empty (i.e., unpacked), but is preferably filled with a suitable packing such as MonelTM or HastelloyTM nickel alloy turnings or wool, or other material inert to HCl and HF which allows efficient mixing (and partial reaction) of the step(b) halopropane starting material(s) and HF vapor.
- the pre-reactor When feeding the halopropane starting material(s) to the pre-reactor as liquid(s), it is preferable for the pre-reactor to be oriented vertically with CF 3 CH 2 CCl y X 3 ⁇ y entering the top of the reactor and pre-heated HF vapor introduced at the bottom of the reactor.
- Temperatures for the pre-reactor are typically within the range of from about 80° C. to about 250° C., and preferably are within the range of from about 100° C. to about 200° C. Under these conditions, for example, CF 3 CH 2 CCl 3 may be converted to a mixture containing predominantly CF 3 CH 2 CCl 2 F.
- the starting material feed rate is ordinarily determined by the length and diameter of the reactor, the temperature, and the degree of fluorination desired within the pre-reactor. Slower feed rates at a given temperature will increase contact time and tend to increase the amount of conversion of the starting material and increase the degree of fluorination of the products.
- degree of fluorination means the extent to which fluorine atoms replace chlorine substituents in the CF 3 CH 2 CCl y X 3 ⁇ y starting materials.
- CF 3 CH 2 CClF 2 represents a higher degree of fluorination than CF 3 CH 2 CCl 3 .
- the molar ratio of HF fed to the pre-reactor, or otherwise to the reaction zone, to CF 3 CH 2 CCl y X 3 ⁇ y starting material(s), is typically from about stoichiometric to about 50:1.
- the stoichiometric ratio depends on the average degree of fluorination of the halopropane starting material(s) and is typically based on formation of CF 3 CH 2 CF 3 . For example, when y is 3, the stoichiometric ratio of HF to CF 3 CH 2 CCl y X 3 ⁇ y is 3:1.
- the stoichiometric ratio of HF to CF 3 CH 2 CCl y X 3 ⁇ y is 2:1. If the average value of y in the halopropane starting materials is 1, the stoichiometric ratio of HF to CF 3 CH 2 CCl y X 3 ⁇ y is 1:1.
- the molar ratio of HF to halopropane starting material is from about twice the stoichiometric ratio (based on formation of CF 3 CH 2 CF 3 ) to about 30:1. Higher ratios of HF to CF 3 CH 2 CCl y X 3 ⁇ y may not be particularly beneficial. Lower ratios can result in reduced yields of CF 3 CH 2 CF 3 .
- the halopropane starting materials are vaporized, preferably in the presence of HF, and contacted with HF in a pre-reactor and the pre-reactor effluent is then contacted with the fluorination catalyst. If the preferred amount of HF is fed in the pre-reactor, additional HF is not required when the effluent from the pre-reactor contacts the fluorination catalyst.
- Temperatures for catalytic fluorination of the CF 3 CH 2 CCl y X 3 ⁇ y starting material (and/or the products formed in a pre-reactor) are typically within the range of from about 200° C. to about 450° C., and preferably are in the range of from about 250° C. to about 400° C., depending on the desired conversion of the starting material and the activity of the catalyst. Reactor temperatures greater than about 400° C. may result in the formation of small amounts of unsaturated by-products. Reactor temperatures below about 240° C. may result in a substantial yield of products with a degree of fluorination less than six (i.e., underfluorinates).
- Reactor pressures for vapor phase embodiments of step (b) may be in the range of from about 1 to about 30 atmospheres. Reactor pressures of about 5 atmospheres to about 20 atmospheres may be advantageously employed to facilitate separation of HCl from other reaction products after the fluorination.
- vapor phase embodiments of step (b) are carried out at least in part in a reactor that contains a catalyst.
- Catalysts which may be used in the preferred vapor phase embodiments of the invention include metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); alumina; fluorided alumina; aluminum fluoride; metals supported on alumina; metals supported on aluminum fluoride; magnesium fluoride supported on aluminum fluoride; metals supported on fluorided alumina; alumina supported on carbon; aluminum fluoride supported on carbon; fluorided alumina supported on carbon; metals supported on carbon; and mixtures of metals, aluminum fluoride, and graphite.
- Suitable metals for use in catalyst compositions include chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc, and/or metals having an atomic number of 58 through 71 (i.e., the lanthanide metals).
- the total metal content of the catalyst will be from about 0.1 to 20 percent by weight; typically from about 0.1 to 10 percent by weight.
- Preferred fluorination catalysts include chromium catalysts (e.g., Cr 2 O 3 by itself or with other metals such as magnesium halides or zinc halides on Cr 2 O 3 ); chromium (III) halides supported on carbon; mixtures of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite; and mixtures of chromium and cobalt (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite, alumina, or aluminum halides such as aluminum fluoride.
- chromium catalysts e.g., Cr 2 O 3 by itself or with other metals such as magnesium halides or zinc halides on Cr 2 O 3
- chromium (III) halides supported on carbon chromium (III) halides supported on carbon
- mixtures of chromium and magnesium including elemental metals, metal oxides, metal
- Catalysts comprising chromium are well known in the art (see e.g., U.S. Pat. No. 5,036,036). Chromium supported on alumina can be prepared as described in U.S. Pat. No. 3,541,834. Chromium supported on carbon can be prepared as described in U.S. Pat. No. 3,632,834. Catalysts comprising chromium and magnesium may be prepared as described in Canadian Patent No. 2,025,145. Other metals and magnesium optionally on graphite can be prepared in a similar manner to the latter patent.
- Preferred chromium catalysts comprise trivalent chromium.
- Cr 2 O 3 prepared by pyrolysis of (NH 4 ) 2 Cr 2 O 7 , Cr 2 O 3 having a surface area greater than about 200 m 2 /g, and chromium chloride supported on carbon having a surface area greater than about 200 m 2 /g some of which are commercially available.
- the Cr 2 O 3 catalyst prepared by the pyrolysis of ammonium dichromate suitable for the process of this invention can be prepared by any method known to the art including those disclosed in U. S. Pat. Nos. 4,843,181 and 5,036,036 which are hereby incorporated herein by reference.
- the catalyst compositions will be pretreated with a fluorinating agent prior to use as catalysts for changing the fluoride content of halogenated carbon compounds.
- a fluorinating agent is HF though other materials may be used such as sulfur tetrafluoride, boron trifluoride, carbonyl fluoride, and fluorinated carbon compounds such as trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, trifluoromethane, or 1,1,2-trichlorotrifluoroethane.
- This pretreatment can be accomplished, for example, by placing the catalyst in a suitable container which can be the reactor to be used to perform the process in the instant invention, and thereafter, passing HF over the catalyst so as to partially saturate the catalyst with HF.
- a suitable container which can be the reactor to be used to perform the process in the instant invention
- passing HF over the catalyst so as to partially saturate the catalyst with HF.
- This is conveniently carried out by passing HF over the catalyst for a period of time, for example, about 0.1 to about 10 hours at a temperature of, for example, about 200° C. to about 450° C. Nevertheless, this pretreament is not essential.
- the product of the step (b) fluorination includes CF 3 CH 2 CF 3 (HFC-236fa).
- Halopropane by-products having lower degrees of fluorination than HFC-236fa that may be present in a product mixture of step (b) include CF 3 CH 2 CClF 2 (HCFC-235fa) and CF 3 CH 2 CCl 2 F (HCFC-234fb). In one embodiment of this invention, these under fluorinated by-products may be returned to the reaction zone of step (b).
- Halopropane by-products having higher degrees of halogenation than HFC-236fa that may be present in the product of step (b) include CF 3 CHClCF 3 (HCFC-226da).
- Halopropene by-products that may be present in the product of step (b) include CF 3 CH ⁇ CF 2 (HFC-1225zc), isomers of C 3 HClF 4 (HCFC-1224) such as CF 3 CH ⁇ CClF (HCFC-1224zb), isomers of C 3 HCl 2 F 3 (HCFC-1223) such as CF 3 CH ⁇ CCl 2 (HCFC-1223za), or CF 3 CH ⁇ CHCl (HCFC-1233zd).
- the effluent from the reaction zone of step (b) may be delivered to one or more distillation columns in which HCl, HF, halopropane by-products having lower degrees of fluorination than HFC-236fa, halopropane by-products having higher degrees of halogenation than HFC-236fa, and halopropene by-products are separated from HFC-236fa and/or the azeotrope of HFC-236fa with HF.
- the HFC-236fa can be recovered from the HF azeotrope by methods known in the art, such as extractive distillation.
- the CF 3 CH 2 CF 3 recovered from step (c) may also be separated from HF by washing the mixture with water optionally followed by washing with a dilute solution or dispersion of an aqueous base such as caustic.
- HF may be removed from HFC-236fa by reaction as disclosed in U.S. Pat. No. 6,224,781.
- the reactor, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the process of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride.
- Typical materials of construction, well-known to the fluorination art include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as MonelTM nickel-copper alloys, HastelloyTM nickel-based alloys and, InconelTM nickel-chromium alloys, and copper-clad steel.
- LEGEND 113 is CClF 2 CCl 2 F 113a is CF 3 CCl 3 133a is CF 3 CH 2 Cl 215aa is CF 3 CCl 2 CClF 2 225da is CF 3 CHClCClF 2 234 is C 3 H 2 Cl 2 F 4 234fb is CF 3 CH 2 CCl 2 F 235fa is CF 3 CH 2 CClF 2 236fa is CF 3 CH 2 CF 3 245fa is CF 3 CH 2 CHF 2 1223 is C 3 HCl 2 F 3 1224 is C 3 HClF 4 1225zc is CF 2 ⁇ CHCF 3
- a 35 mL PyrexTM glass flanged reactor equipped with internal cooling coils, a Claisen adapter, condenser, a TC well, a PTFE-coated stirring bar, and a chlorine inlet tube was charged with 33.0 g of carbon tetrachloride.
- the top of the condenser was connected in series to a bubbler containing Krytox® oil and a KOH scrubber.
- the reactor cooling coil and condenser were connected to a small chiller recirculating water/ethylene glycol at a temperature of about ⁇ 9° C. After the reactor was cooled, about 9 g (0.067 mole) of HFC-245fa were added to the reactor from a cylinder.
- the reactor was purged with nitrogen and irradiated with a 275W SylvaniaTM sunlamp. Chlorine gas was fed subsurface into the reactor solution from a rotameter at a rate of about 20 sccm (3.4 ⁇ 10 ⁇ 7 m 3 /s). The temperature in the reactor during the chlorination was about 3-5° C. After 1 hour the chlorine feed and irradiation were stopped. Analysis of the reaction solution by GC-MS indicated that the product was substantially 235fa. After washing the product with aqueous 10% sodium bisulfite, a total of 32 g of product were obtained.
- the 35 mL reactor was purged with nitrogen with cooling applied to the coils.
- the reactor was then charged with about 30 g (0.224 mole) of HFC-245fa.
- the reactor was purged briefly with nitrogen and then irradiated with a 275W SylvaniaTM sunlamp.
- Chlorine gas was fed subsurface to the reactor from a rotameter at a rate of about 20 sccm (3.4 ⁇ 10 ⁇ 7 m 3 /s); the temperature in the reactor during the chlorination was about 2-3° C. After about 3 hours, there was noticeable chlorine break-through; the chlorine feed and irradiation were then stopped.
- Analysis of the reaction product by GC-MS indicated that the product was about 97% 235fa. After washing the product with aqueous 10% sodium bisulfite, a total of 16 g of product were obtained.
- the reaction product was analyzed by GC-MS; the principal products are summarized in TABLE I.
- a 91.4 cm length of PyrexTM glass tubing was formed in a coil about 8 cm in diameter; the tubing had an inner diameter of 0.395 cm and a wall thickness of about 1.2 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 17 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE II.
- Example above was repeated using a 91.4 cm length of TeflonTM PFA tubing which was formed in a coil about 14 cm in diameter; the tubing had an inner diameter of 0.32 cm and a wall thickness of about 1.6 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 11 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE III.
- Example above was repeated using a 45.7 cm length of NafionTM tubing which was formed in a coil about 8 cm in diameter; the tubing had an inner diameter of 0.14 cm and a wall thickness of about 0.13 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 6 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE IV.
- the 20% CrCl 3 on carbon catalyst prepared above (3.12 g, 8 mL, 6 to 8 mesh, (2.36 to 3.35 mm)) was placed in a 5 ⁇ 8′′ (1.58 cm) diameter InconelTM nickel alloy reactor tube heated in a fluidized sand bath.
- the catalyst was heated from 53° C. to 177° C. in a flow of nitrogen (50 sccm, 8.4 ⁇ 10 ⁇ 7 m 3 /s) over the course of about one hour.
- HF was then admitted to the reactor at a flow rate of 50 sccm (8.4 ⁇ 10 ⁇ 7 m 3 /s).
- a 15 in ⁇ 3 ⁇ 8 in Inconel® tube was filled with 1.64 grams (1.5 cc) of a high surface area chrome oxide gel catalyst (>200 m 2 /gm) ground to 20-30 mesh (0.60 to 0.85 mm).
- the catalyst was activated by first drying at 400° C. for 0.33 hours under a nitrogen purge (38 sccm, 6.3 ⁇ 10 ⁇ 7 m 3 s). The temperature was lowered to 300° C., and the HF flow was begun (15 sccm, 2.5 ⁇ 10 ⁇ 7 m 3 /s) and the nitrogen flow was reduced (25 sccm, 4.2 ⁇ 10 ⁇ 7 m 3 /s). After 35 minutes the temperature was raised to 325° C. for 60 minutes, to 350° C.
- the flow of HF was set to 26 sccm (4.3 ⁇ 10 ⁇ 7 m 3 /s) while the nitrogen flow was set to 16 sccm (4.2 ⁇ 10 ⁇ 7 m 3 /s).
- the HF flow was increased to 38 sccm (6.3 ⁇ 10 ⁇ 7 m 3 /s) and the nitrogen decreased to 11 sccm.
- the HF flow was maintained at 38 sccm (6.3 ⁇ 10 ⁇ 7 m 3 /s) while the nitrogen flow was decreased to 11 sccm (1.8 ⁇ 10 ⁇ 7 m 3 /s).
- the nitrogen flow was increased to 78 sccm (1.3 ⁇ 10 ⁇ 6 m 3 /s).
- the HF flow was increased to 62 sccm (1.0 ⁇ 10 ⁇ 6 m 3 /s) and the nitrogen was set to 1 sccm (1.7 ⁇ 10 ⁇ 8 m 3 /s). This condition was maintained for two hours, and then the temperature of the reactor was cooled to 190° C.
- a 15 in ⁇ 3 ⁇ 8 in Inconel® tube was filled with 1.95 grams (1.5 cc) of a chromium oxide catalyst made via the pyrolysis of ammonium dichromate ground to 20-30 mesh.
- the catalyst was activated by first drying at 400° C. under a nitrogen purge followed by treatment with HF as described in EXAMPLES 10-12
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Abstract
A process for the preparation of 1,1,1,3,3,3-hexafluoropropane is disclosed. The process involves (a) contacting at least one halopropane of the formula CF3CH2CHyX3-y (where each X is independently F, Cl or Br, and y is 3, 2, or 1) with Cl?2#191 in the presence of light or a free radical initiator to produce a mixture comprising CF3CH2CCIyX3-y; (b) contacting the CF3CH2CCIyX3-y produced in step (a) with HF, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CF3CH2CF3; and (c) recovering CF3CH2CF3 from the mixture produced in step (b).
Description
This application represents a national filing under 35 U.S.C. 371 of International Application No. PCT/US2005/046264 filed Dec. 19, 2005, and claims priority of U.S. Provisional Application No. 60/638,277 filed Dec. 22, 2004.
The present invention relates to the synthesis of 1,1,1,3,3,3-hexafluoropropane.
Commercial methods for the preparation of 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3 or HFC-236fa), a fire extinguishant and refrigerant, involve fluorination of 1,1,1,3,3,3-hexachloropropane (CCl3CH2CCl3 or HCC-230fa) in the liquid phase (see for e.g., U.S. Pat. No. 6,291,730), in the vapor phase (see e.g., U.S. Pat. Nos. 5,414,165 and 5,545,774), or a combination of liquid and vapor phase processes (see U.S. Pat. No. 6,066,769). U.S. Pat. No. 5,573,654 reports the preparation of HFC-236fa by the reaction of perfluoroisobutylene with triethylamine and water.
This invention provides a process for the preparation of 1,1,1,3,3,3-hexafluoropropane. The process comprises (a) contacting at least one halopropane of the formula CF3CH2CHyX3−y (where each X is independently selected from the group consisting of F, Cl and Br, and y is 3, 2, or 1) with chlorine (Cl2) in the presence of light or a free radical initiator to produce a mixture comprising CF3CH2CClyX3-y; (b) contacting the CF3CH2CClyX3−y produced in step (a) with HF, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CF3CH2CF3; and (c) recovering CF3CH2CF3 from the mixture produced in step (b).
This invention provides a process for the preparation of 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa) from readily available starting materials.
In step (a) of the process of this invention, one or more halopropane compounds CF3CH2CHyX3-y, where each X is independently F, Cl, or Br, and y is 3, 2, or 1, are contacted with chlorine (Cl2) in the presence of an initiator. Typically, the reaction of halopropane starting material(s) with chlorine is carried out in a reaction zone operated to provide substantial substitution of chlorine for the end-carbon hydrogens of the halopropane starting material(s) without substantial replacement of hydrogens on the middle carbon. Typically at least 90%, and preferably greater than 95%, of the hydrogens of the CF3CH2CHyX3−y starting material replaced during step (a) are end carbon hydrogens. Free radical initiators such as peroxides or azo compounds may be employed. Preferably, chlorine radicals are generated by the action of light on Cl2 (i.e., photochlorination is preferably used).
Suitable halopropane starting materials for step (a) include CF3CH2CHF2 (HFC-245fa), CF3CH2CHClF (HCFC-244fa), CF3CH2CHCl2 (HCFC-243fa), CF3CH2CH2Cl (HCFC-253fb), CF3CH2CH2Br (HCFC-253fbB), CF3CH2CH2F (HFC-254fb), and CF3CH2CH3 (HFC-263fb). Due to their availability, CF3CH2CHF2 (HFC-245fa), CF3CH2CH2Cl (HCFC-253fb), and CF3CH2CH3 (HFC-263fb) are generally preferred.
1,1,1,3,3-Pentafluoropropane (HFC-245fa) may be prepared by fluorination of HCC-240fa as described in U.S. Pat. No. 6,291,730. HCFC-253fb may be prepared by fluorination of 1,1,1,3-tetrachloropropane as disclosed in U.S. Pat. No. 4,078,007. HFC-263fb may be prepared by hydrogenation of 3,3,3-trifluoropropene as disclosed by Haszeldine in Journal of the Chemical Society, 1952, page 2510.
The photochlorination of the halopropane starting materials of the formula CF3CH2CHyX3−y may be carried out in either the liquid or the vapor phase. For vapor phase photochlorination, initial contact of the starting materials with Cl2 may be a continuous process in which one or more starting materials are vaporized (optionally in the presence of an inert carrier gas, such as nitrogen, argon, or helium) and contacted with chlorine vapor in a reaction zone. A suitable photochlorination reaction zone is one in which light having a wavelength of from about 250 nm to about 400 nm can irradiate the reaction components for a time sufficient to convert at least a portion of the halopropane starting materials to CF3CH2CClyX3-y. The source of light may be any one of a number of arc or filament lamps known in the art. Light having the desired wavelength may introduced into the reaction zone by a number of means. For example, the light may enter the reaction zone through a lamp well or window fabricated from a material suitably transparent to light having a wavelength of from about 250 nm to about 400 nm. Likewise, the walls of the reaction zone may be fabricated from such a material so that at least a portion of the light used for the photochlorination can be transmitted through the walls. Examples of suitable materials include quartz, glass, or fluoropolymers such as poly(tetrafluoroethylene) (e.g., Teflon® fluoropolymer), copolymers of perfluoro(alkyl vinyl ethers) (e.g., polyfluoroalkoxy resins such as Teflon® PFA fluoropolymer), and functionalized copolymers of terminally functionalized perfluoro(alkyl vinyl ethers) (e.g., perfluorosulfonic acid resins such as Nafion® fluoropolymer). Further details of photochlorination using polymeric materials such as Teflon® fluoropolymer, Teflon® PFA fluoropolymer, and Nafion® fluoropolymer are disclosed in U.S. patent application Ser. Nos. 60/638289, 60/638292, 60/638290 and 60/638293 all of which were filed Dec. 22, 2004, and are incorporated herein by reference. Of note are embodiments where the chlorination step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from poly(tetrafluoroethylene), a copolymer of perfluoro(alkyl vinyl ether), or a functionalized copolymer of a terminally functionalized perfluoro(alkyl vinyl ether), and light is transmitted through said polymeric portion.
The portion of the reactor wall fabricated from such polymeric materials may be limited to a fraction of the reactor wall (e.g., a window of the polymeric material positioned in a reactor principally fabricated from another material) or may constitute all or essentially all of the reactor wall (e.g., a tube reactor fabricated from the polymeric material).
Alternatively, the process of the invention may be carried out in the liquid phase by feeding Cl2 to a reactor containing the halopropane starting materials. Suitable liquid phase reactors include vessels fabricated from glass in which an external lamp is directed toward the reactor and metal or glass-lined metal reactors having one or more wells or windows for introducing light having a suitable wavelength. Also suitable are fluoropolymer-lined metal reactors having one or more wells or windows for introducing light having a suitable wavelength. Preferably the reactor is provided with a condenser or other means of keeping the halopropane starting materials being irradiated to be in the liquid state in the reactor while permitting the hydrogen chloride (HCl) released during the chlorination to escape the reactor.
In some embodiments it may be advantageous to conduct the photochlorination in the presence of a solvent capable dissolving one or more of the halopropane starting materials and/or step (a) products. Preferred solvents include those that do not have easily replaceable hydrogen substituents. Examples of solvents suitable for step (a) include carbon tetrachloride, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1,1,2-trichlorotrifluoroethane, benzene, chlorobenzene, dichlorobenzene, fluorobenzene, and difluorobenzene.
Suitable temperatures for the photochlorination of the halopropane starting materials of the formula CF3CH2CHyX3−y are within the range of from about −20° C. to about 60° C. Preferred temperatures are typically within the range of from about 0° C. to about 40° C. In the liquid phase embodiment of step (a), it is convenient to control the reaction temperature so that starting material is primarily in the liquid phase; that is, at a temperature that is below the boiling point of the step (a) halopropane starting material(s) and product(s).
The pressure of step (a) in a liquid phase process is not critical so long as the liquid phase is maintained. Unless controlled by means of a suitable pressure-regulating device, the pressure of the system increases as hydrogen chloride is formed during step (a) by replacement of hydrogen substituents in the starting material by chlorine substituents. In a continuous or semi-batch process it is possible to set the pressure of the reactor in such a way that the HCl produced in the reaction is vented from the reactor (optionally through a packed column or condenser). Typical reactor pressures are from about 14.7 psig (101.3 kPa) to about 50 psig (344.6 kPa).
The amount of chlorine (Cl2) fed to the reactor is based on the value of y in CF3CH2CHyX3-y. The ratio of Cl2 to halopropane starting material is typically the stoichiometric amount required to substitute the hydrogen in the CHyX3−y Y group with a chlorine atom. For example, when y is 3, the molar ratio of Cl2 to CF3CH2CHyX3−y is preferably about 3:1; when y is 2, the molar ratio of Cl2 to CF3CH2CHyX3−y is preferably about 2:1; and when y is 1, the molar ratio of Cl2 to CF3CH2CHyX3−y is preferably about 1:1. A slight excess of chlorine over the stoichiometric amount may be desirable to facilitate conversion, but feeding a large excess chlorine to the reactor can result in a higher degree of halogenation in the products than is desirable.
Examples of compounds that can be produced in step (a), particularly by photochlorination, include CF3CH2CCl3 (HCFC-233fb, produced from CF3CH2CHyX3−y starting material where y is 3, 2, or 1 and X is Cl), CF3CH2CBrCl2 (HCFC-233fbB, produced from CF3CH2CHyX3−y starting material where y is 2 and X is Br), CF3CH2CCl2F (HCFC-234fb, produced from CF3CH2CHyX3−y starting material where y is 2 and X is F, or where y is 1, one X is Cl and the other X is F), and CF3CH2CClF2 (HCFC-235fa, produced from CF3CH2CHyX3−y starting material where y is 1 and X is F).
Under-chlorinated halopropane by-products that may be formed include compounds in which the value of y in CF3CH2CHyX3−y has been reduced from 3 to 2, from 3 to 1, or from 2 to 1.
Over-chlorinated halopropane by-products that may be produced include halopropanes of the formula CF3CH2-wClwCClyX3−y where w=1 or 2, such as for example, CF3CHClCClF2 (HCFC-225da), CF3CCl2CClF2 (CFC-215aa), CF3CHClCCl2F (HCFC-224db), CF3CCl2CCl2F (CFC-214ab), CF3CHClCCl3 (HCFC-223ab), and CF3CCl2CCl3 (CFC-213ab).
If desired, the effluent from step (a) may be subjected to one or more purification steps where the desired product, CF3CH2CClyX3−y, is separated from HCl, under-chlorinated halopropane by-products, unreacted halopropane starting materials, and over-chlorinated halopropane by-products by distillation. In one embodiment of the invention unreacted halopropane starting materials and under-chlorinated halopropane by-products may be recovered and returned to step (a).
In step (b) of the process of the invention, the CF3CH2CClyX3−y produced in step (a) is contacted with HF, optionally in the presence of a fluorination catalyst, to produce a mixture comprising CF3CH2CF3. Step (b) of the process of the invention may take place in either liquid or the vapor phase.
In the liquid phase embodiment of step (b), the reactor effluent from step (a) or the separated CF3CH2CClyX3−y produced in step (a), is contacted with anhydrous hydrogen fluoride (HF) to form a mixture of fluorinated compounds. The contacting of CF3CH2CClyX3−y and HF may be conducted in the liquid phase in one of several ways. The process of the invention may be conducted in batch, semi-continuous, or continuous modes. In the batch mode, the CF3CH2CClyX3−y step (b) starting material and hydrogen fluoride are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature. Preferably, liquid step (b) starting material of the formula CF3CH2CClyX3−y is fed to a reactor containing liquid HF, or a liquid mixture of HF and fluorinated compounds formed by reacting HF with CF3CH2CClyX3−y starting material, held at the desired reaction temperature. Alternatively, liquid HF may be fed to a reactor containing CF3CH2CClyX3−y starting material, or a mixture of CF3CH2CClyX3−y starting material and a mixture of fluorinated compounds formed by reacting HF with the CF3CH2CClyX3−y starting material.
In another embodiment, both HF and CF3CH2CClyX3−y starting material may be fed concurrently as liquids in the desired stoichiometric ratio to a reactor containing a mixture of HF and fluorinated compounds formed by reacting HF with CF3CH2CClyX3-y.
In the liquid phase embodiment of step (b) of the process, the CF3CH2CClyX3−y starting materials are preferably reacted with HF in the presence of fluorination catalysts selected from the halides, oxides, or oxyhalides of one or more metal compounds. Said metals may be selected from the group consisting of boron, aluminum, tin, titanium, vanadium, iron, zinc, arsenic, antimony, molybdenum, tungsten, niobium, and tantalum, and mixtures thereof. Said halides, oxides, or oxyhalides of one or more metal compounds may optionally be supported on carbon. Of note are fluorination catalyst compositions selected from the group consisting of AlF3, BF3, FeCl3-aFa (where a is 0 to 3), FeZ3 (where Z is halogen) supported on carbon, SbCl3-aFa, AsF3, MCl5-bFb (where b is 0 to 5 and M is Sb, Nb, Ta, or Mo), and M′Cl4-cFc (where c is 0 to 4, and M′ is Sn, Ti, Zr, or Hf). Preferred fluorination catalyst compositions for the liquid phase embodiment of step (b) are those containing metal halides selected from the group antimony, tin, niobium, and tantalum.
Other fluorination catalyst compositions useful for liquid phase step (b) embodiments include halides, fluorosulfonates or triflates of antimony, molybdenum, niobium, tantalum, tin or titanium as disclosed in U.S. Pat. No. 5,773,637.
The temperature of the liquid phase embodiment of step (b) can be in the range of 50° C. to 175° C., preferably, 60° C. to 150° C. The pressure is selected so that the reaction medium is maintained in the liquid state.
The pressure of the system increases as hydrogen chloride or hydrogen bromide are formed by replacement of chlorine or bromine substituents for fluorine subsituents in the CF3CH2CClyX3−y starting materials and as the volatility of the organic components increases due to the formation of CF3CH2CF3. In a continuous process it is possible to set the pressure of the reactor in such a way that the HCl or HBr liberated by the reaction is vented from the reactor. Typical reaction pressures are from about 20 psig (137.8 kPa) to about 1000 psig (6891 kPa).
The molar ratio of HF to CF3CH2CClyX3−y starting materials employed in the liquid phase embodiment of step (b) is typically from about 1:1 to about 100:1, preferably from about 3:1 to about 50:1 and most preferably from about 3:1 to about 30:1.
The step (b) reaction of HF with CF3CH2CClyX3−y can also be carried out in the vapor phase (e.g., in a heated tubular reactor). For tubular reactors, a number of reactor configurations are possible, including horizontal or vertical orientation of the reactor and different modes of contacting the starting halopropanes with HF. Preferably the HF is substantially anhydrous.
The step (b) starting material(s) may be fed to a reactor containing a fluorination catalyst. For example, the halopropane starting material(s) may be initially vaporized and the vaporized starting materials and HF may be directly fed to a reaction zone containing a fluorination catalyst as gas(es).
Alternatively, the step (b) halopropane starting material(s) may be contacted with HF in a pre-reactor. The pre-reactor may be empty (i.e., unpacked), but is preferably filled with a suitable packing such as Monel™ or Hastelloy™ nickel alloy turnings or wool, or other material inert to HCl and HF which allows efficient mixing (and partial reaction) of the step(b) halopropane starting material(s) and HF vapor.
When feeding the halopropane starting material(s) to the pre-reactor as liquid(s), it is preferable for the pre-reactor to be oriented vertically with CF3CH2CClyX3−y entering the top of the reactor and pre-heated HF vapor introduced at the bottom of the reactor.
Temperatures for the pre-reactor are typically within the range of from about 80° C. to about 250° C., and preferably are within the range of from about 100° C. to about 200° C. Under these conditions, for example, CF3CH2CCl3 may be converted to a mixture containing predominantly CF3CH2CCl2F. The starting material feed rate is ordinarily determined by the length and diameter of the reactor, the temperature, and the degree of fluorination desired within the pre-reactor. Slower feed rates at a given temperature will increase contact time and tend to increase the amount of conversion of the starting material and increase the degree of fluorination of the products. The term “degree of fluorination” means the extent to which fluorine atoms replace chlorine substituents in the CF3CH2CClyX3−y starting materials. For example, CF3CH2CClF2 represents a higher degree of fluorination than CF3CH2CCl3.
The molar ratio of HF fed to the pre-reactor, or otherwise to the reaction zone, to CF3CH2CClyX3−y starting material(s), is typically from about stoichiometric to about 50:1. The stoichiometric ratio depends on the average degree of fluorination of the halopropane starting material(s) and is typically based on formation of CF3CH2CF3. For example, when y is 3, the stoichiometric ratio of HF to CF3CH2CClyX3−y is 3:1. If the average value of y in the halopropane starting materials is 2, the stoichiometric ratio of HF to CF3CH2CClyX3−y is 2:1. If the average value of y in the halopropane starting materials is 1, the stoichiometric ratio of HF to CF3CH2CClyX3−y is 1:1. Preferably, the molar ratio of HF to halopropane starting material is from about twice the stoichiometric ratio (based on formation of CF3CH2CF3) to about 30:1. Higher ratios of HF to CF3CH2CClyX3−y may not be particularly beneficial. Lower ratios can result in reduced yields of CF3CH2CF3.
In a preferred embodiment of step (b), the halopropane starting materials are vaporized, preferably in the presence of HF, and contacted with HF in a pre-reactor and the pre-reactor effluent is then contacted with the fluorination catalyst. If the preferred amount of HF is fed in the pre-reactor, additional HF is not required when the effluent from the pre-reactor contacts the fluorination catalyst.
Temperatures for catalytic fluorination of the CF3CH2CClyX3−y starting material (and/or the products formed in a pre-reactor) are typically within the range of from about 200° C. to about 450° C., and preferably are in the range of from about 250° C. to about 400° C., depending on the desired conversion of the starting material and the activity of the catalyst. Reactor temperatures greater than about 400° C. may result in the formation of small amounts of unsaturated by-products. Reactor temperatures below about 240° C. may result in a substantial yield of products with a degree of fluorination less than six (i.e., underfluorinates).
Reactor pressures for vapor phase embodiments of step (b) may be in the range of from about 1 to about 30 atmospheres. Reactor pressures of about 5 atmospheres to about 20 atmospheres may be advantageously employed to facilitate separation of HCl from other reaction products after the fluorination.
Preferably, vapor phase embodiments of step (b) are carried out at least in part in a reactor that contains a catalyst. Catalysts which may be used in the preferred vapor phase embodiments of the invention include metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); alumina; fluorided alumina; aluminum fluoride; metals supported on alumina; metals supported on aluminum fluoride; magnesium fluoride supported on aluminum fluoride; metals supported on fluorided alumina; alumina supported on carbon; aluminum fluoride supported on carbon; fluorided alumina supported on carbon; metals supported on carbon; and mixtures of metals, aluminum fluoride, and graphite.
Suitable metals for use in catalyst compositions (optionally on alumina, aluminum fluoride, fluorided alumina, or carbon) include chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc, and/or metals having an atomic number of 58 through 71 (i.e., the lanthanide metals). Preferably when used on a support, the total metal content of the catalyst will be from about 0.1 to 20 percent by weight; typically from about 0.1 to 10 percent by weight.
Preferred fluorination catalysts include chromium catalysts (e.g., Cr2O3 by itself or with other metals such as magnesium halides or zinc halides on Cr2O3); chromium (III) halides supported on carbon; mixtures of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite; and mixtures of chromium and cobalt (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite, alumina, or aluminum halides such as aluminum fluoride.
Catalysts comprising chromium are well known in the art (see e.g., U.S. Pat. No. 5,036,036). Chromium supported on alumina can be prepared as described in U.S. Pat. No. 3,541,834. Chromium supported on carbon can be prepared as described in U.S. Pat. No. 3,632,834. Catalysts comprising chromium and magnesium may be prepared as described in Canadian Patent No. 2,025,145. Other metals and magnesium optionally on graphite can be prepared in a similar manner to the latter patent.
Preferred chromium catalysts comprise trivalent chromium. Of note is Cr2O3 prepared by pyrolysis of (NH4)2Cr2O7, Cr2O3 having a surface area greater than about 200 m2/g, and chromium chloride supported on carbon having a surface area greater than about 200 m2/g some of which are commercially available.
The Cr2O3 catalyst prepared by the pyrolysis of ammonium dichromate suitable for the process of this invention can be prepared by any method known to the art including those disclosed in U. S. Pat. Nos. 4,843,181 and 5,036,036 which are hereby incorporated herein by reference.
Typically, the catalyst compositions will be pretreated with a fluorinating agent prior to use as catalysts for changing the fluoride content of halogenated carbon compounds. Typically this fluorinating agent is HF though other materials may be used such as sulfur tetrafluoride, boron trifluoride, carbonyl fluoride, and fluorinated carbon compounds such as trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, trifluoromethane, or 1,1,2-trichlorotrifluoroethane. This pretreatment can be accomplished, for example, by placing the catalyst in a suitable container which can be the reactor to be used to perform the process in the instant invention, and thereafter, passing HF over the catalyst so as to partially saturate the catalyst with HF. This is conveniently carried out by passing HF over the catalyst for a period of time, for example, about 0.1 to about 10 hours at a temperature of, for example, about 200° C. to about 450° C. Nevertheless, this pretreament is not essential.
The product of the step (b) fluorination includes CF3CH2CF3 (HFC-236fa). Halopropane by-products having lower degrees of fluorination than HFC-236fa that may be present in a product mixture of step (b) include CF3CH2CClF2 (HCFC-235fa) and CF3CH2CCl2F (HCFC-234fb). In one embodiment of this invention, these under fluorinated by-products may be returned to the reaction zone of step (b).
Halopropane by-products having higher degrees of halogenation than HFC-236fa that may be present in the product of step (b) include CF3CHClCF3 (HCFC-226da).
Halopropene by-products that may be present in the product of step (b) include CF3CH═CF2 (HFC-1225zc), isomers of C3HClF4 (HCFC-1224) such as CF3CH═CClF (HCFC-1224zb), isomers of C3HCl2F3 (HCFC-1223) such as CF3CH═CCl2 (HCFC-1223za), or CF3CH═CHCl (HCFC-1233zd).
In step (c) of the process of the invention, the effluent from the reaction zone of step (b) may be delivered to one or more distillation columns in which HCl, HF, halopropane by-products having lower degrees of fluorination than HFC-236fa, halopropane by-products having higher degrees of halogenation than HFC-236fa, and halopropene by-products are separated from HFC-236fa and/or the azeotrope of HFC-236fa with HF. The HFC-236fa can be recovered from the HF azeotrope by methods known in the art, such as extractive distillation.
The CF3CH2CF3 recovered from step (c) may also be separated from HF by washing the mixture with water optionally followed by washing with a dilute solution or dispersion of an aqueous base such as caustic.
Alternatively, HF may be removed from HFC-236fa by reaction as disclosed in U.S. Pat. No. 6,224,781.
The reactor, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the process of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.
Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.
LEGEND |
113 is CClF2CCl2F | 113a is CF3CCl3 | ||
133a is CF3CH2Cl | 215aa is CF3CCl2CClF2 | ||
225da is CF3CHClCClF2 | 234 is C3H2Cl2F4 | ||
234fb is CF3CH2CCl2F | 235fa is CF3CH2CClF2 | ||
236fa is CF3CH2CF3 | 245fa is CF3CH2CHF2 | ||
1223 is C3HCl2F3 | 1224 is C3HClF4 | ||
1225zc is CF2═CHCF3 | |||
A 35 mL Pyrex™ glass flanged reactor equipped with internal cooling coils, a Claisen adapter, condenser, a TC well, a PTFE-coated stirring bar, and a chlorine inlet tube was charged with 33.0 g of carbon tetrachloride. The top of the condenser was connected in series to a bubbler containing Krytox® oil and a KOH scrubber. The reactor cooling coil and condenser were connected to a small chiller recirculating water/ethylene glycol at a temperature of about −9° C. After the reactor was cooled, about 9 g (0.067 mole) of HFC-245fa were added to the reactor from a cylinder. The reactor was purged with nitrogen and irradiated with a 275W Sylvania™ sunlamp. Chlorine gas was fed subsurface into the reactor solution from a rotameter at a rate of about 20 sccm (3.4×10−7 m3/s). The temperature in the reactor during the chlorination was about 3-5° C. After 1 hour the chlorine feed and irradiation were stopped. Analysis of the reaction solution by GC-MS indicated that the product was substantially 235fa. After washing the product with aqueous 10% sodium bisulfite, a total of 32 g of product were obtained.
Following the procedure described above, the 35 mL reactor was purged with nitrogen with cooling applied to the coils. The reactor was then charged with about 30 g (0.224 mole) of HFC-245fa. The reactor was purged briefly with nitrogen and then irradiated with a 275W Sylvania™ sunlamp. Chlorine gas was fed subsurface to the reactor from a rotameter at a rate of about 20 sccm (3.4×10−7 m3/s); the temperature in the reactor during the chlorination was about 2-3° C. After about 3 hours, there was noticeable chlorine break-through; the chlorine feed and irradiation were then stopped. Analysis of the reaction product by GC-MS indicated that the product was about 97% 235fa. After washing the product with aqueous 10% sodium bisulfite, a total of 16 g of product were obtained. The reaction product was analyzed by GC-MS; the principal products are summarized in TABLE I.
TABLE I |
HFC-245fa Photochlorination Products |
Code | Formula | GC Area % | ||
HCFC-235fa | CF3CH2CClF2 | 98.05 | ||
CFC-215aa | CF3CCl2CClF2 | 0.64 | ||
HCFC-225da | CF3CHClCClF2 | 0.42 | ||
HCFC-234 | C3H2Cl2F4 | 0.30 | ||
A 91.4 cm length of Pyrex™ glass tubing was formed in a coil about 8 cm in diameter; the tubing had an inner diameter of 0.395 cm and a wall thickness of about 1.2 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 17 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE II.
TABLE II | |||
Mole | |||
Ratio | Product Analysis, GC Area % |
Ex. No. | Cl2/245fa | 235fa | 245fa | 225da | 215aa | 234 | 133a | 113a |
3 | 1 | 88.5 | 11.0 | 0.2 | 0.05 | 0.02 | 0.01 | 0.1 |
4 | 2 | 98.4 | 0.2 | 0.6 | 0.5 | 0 | 0 | 0.3 |
The Example above was repeated using a 91.4 cm length of Teflon™ PFA tubing which was formed in a coil about 14 cm in diameter; the tubing had an inner diameter of 0.32 cm and a wall thickness of about 1.6 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 11 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE III.
TABLE III | |||
Mole | |||
Ratio | Product Analysis, GC Area % |
Ex. No. | Cl2/245fa | 235fa | 245fa | 225da | 215aa | 234 | 133a | 113a |
5 | 1 | 87.2 | 12.4 | 0.2 | 0.04 | 0.03 | 0.01 | 0.1 |
6 | 2 | 91.8 | 7.6 | 0.2 | 0.04 | 0 | 0.04 | 0.2 |
The Example above was repeated using a 45.7 cm length of Nafion™ tubing which was formed in a coil about 8 cm in diameter; the tubing had an inner diameter of 0.14 cm and a wall thickness of about 0.13 mm. Chlorine gas and HFC-245fa were co-fed to the coil at room temperature; the coil was irradiated with the 275 watt sunlamp. The residence time in the tube was approximately 6 seconds. The effluent from the tube was analyzed by gas chromatography; the results are summarized in the TABLE IV.
TABLE IV | |||
Mole | |||
Ratio | Product Analysis, GC Area % |
Ex. No. | Cl2/245fa | 235fa | 245fa | 225da | 215aa | 234 | 133a | 113a |
7 | 1 | 13.3 | 86.2 | 0 | 0 | 0 | 0.4 | 0.01 |
A commercial sample of 20% CrCl3 on carbon catalyst was used for this work. The preparation and activation procedure of this catalyst is described in U.S. Pat. No. 5,545,774.
The 20% CrCl3 on carbon catalyst prepared above (3.12 g, 8 mL, 6 to 8 mesh, (2.36 to 3.35 mm)) was placed in a ⅝″ (1.58 cm) diameter Inconel™ nickel alloy reactor tube heated in a fluidized sand bath. The catalyst was heated from 53° C. to 177° C. in a flow of nitrogen (50 sccm, 8.4×10−7 m3/s) over the course of about one hour. HF was then admitted to the reactor at a flow rate of 50 sccm (8.4×10−7 m3/s). After 0.5 h the nitrogen flow was decreased to 20 sccm (3.4×10−7 m3s) and the HF flow increased to 80 sccm (1.3×10−8 m3/s). The reactor temperature was then gradually increased to 400° C. over 3 hours. At the end of this period, the HF flow was stopped and the reactor cooled to 175° C. under 20 sccm (3.4×10−7 m3/s) nitrogen flow. The results of the fluorination of HCFC-235fa at 250° C. and 300° C. are shown in TABLE IV below. The contact time was 20 seconds and the mole ratio of HF to HCFC-235fa was 6:1.
TABLE V | ||
Product Analysis, GC Area % |
Ex. No. | Temp | 236fa | 235fa | 1225zc | 226da | 1224 | 1223 | 113 |
8 | 250 | 83.1 | 14.1 | 1.7 | 0.2 | 0.3 | 0.2 | 0.3 |
9 | 300 | 99.1 | 0.07 | 0.1 | 0.2 | 0.02 | 0 | 0.3 |
Catalyst Activation
A 15 in×⅜ in Inconel® tube was filled with 1.64 grams (1.5 cc) of a high surface area chrome oxide gel catalyst (>200 m2/gm) ground to 20-30 mesh (0.60 to 0.85 mm). The catalyst was activated by first drying at 400° C. for 0.33 hours under a nitrogen purge (38 sccm, 6.3×10−7 m3s). The temperature was lowered to 300° C., and the HF flow was begun (15 sccm, 2.5×10−7 m3/s) and the nitrogen flow was reduced (25 sccm, 4.2×10−7 m3/s). After 35 minutes the temperature was raised to 325° C. for 60 minutes, to 350° C. for 60 minutes, 375° C. for 60 minutes, 400° C. for 60 minutes, and 425° C. for 60 minutes. After this period of 60 minutes at 425° C., the flow of HF was set to 26 sccm (4.3×10−7 m3/s) while the nitrogen flow was set to 16 sccm (4.2×10−7 m3/s). After 20 minutes, the HF flow was increased to 38 sccm (6.3×10−7 m3/s) and the nitrogen decreased to 11 sccm. After 20 minutes, the HF flow was maintained at 38 sccm (6.3×10−7 m3/s) while the nitrogen flow was decreased to 11 sccm (1.8×10−7 m3/s). After 20 minutes, the nitrogen flow was increased to 78 sccm (1.3×10−6 m3/s). After 20 minutes, the HF flow was increased to 62 sccm (1.0×10−6 m3/s) and the nitrogen was set to 1 sccm (1.7×10−8 m3/s). This condition was maintained for two hours, and then the temperature of the reactor was cooled to 190° C.
Fluorination of the HCFC Mixture
A mixture of 18.4% CF3CH2CCl2F (HCFC-234fb), 36.2% CF3CH═CCl2 (HCFC-1225za), and 45.4% CCl2FCH2CCl2F (HCFC-232fa) was fed to the above catalyst at 191 to 209° C. The flow rate of the above mixture was 1.8 sccm (3.0×10−8 m3/s) and the flow of HF was 57.6 sccm (9.6×10−7 m3s). Under these conditions, all of the HCFC-234fb and HCFC-232fa reacted. The gas chromatographic analysis of the reactor effluent at three temperatures is given in TABLE VI.
TABLE VI | ||
Product Analysis, | ||
GC Area % |
Ex. No. | Temp., ° C. | 236fa | 235fa | 1223za |
10 | 191 | 93.0 | 6.9 | 0.1 |
11 | 201 | 99.0 | 1.0 | 0 |
12 | 209 | 99.9 | 0.1 | 0 |
Catalyst Activation
A 15 in×⅜ in Inconel® tube was filled with 1.95 grams (1.5 cc) of a chromium oxide catalyst made via the pyrolysis of ammonium dichromate ground to 20-30 mesh. The catalyst was activated by first drying at 400° C. under a nitrogen purge followed by treatment with HF as described in EXAMPLES 10-12
Fluorination of the HCFC Mixture
The mixture used in EXAMPLES 10-12 was fed to the above catalyst at 190 to 210° C. The flow rate of the above mixture was 1.8 sccm (3.0×10−8 m3/s) and the flow of HF was 57.6 sccm (9.6×10−7 m3/s). Under these conditions, all of the HCFC-234fb and HCFC-232fa reacted. The gas chromatographic analysis of the reactor effluent at three temperatures is given in TABLE VII.
TABLE VII | ||
Product Analysis, | ||
GC Area % |
Ex. No. | Temp., ° C. | 236fa | 235fa | %1223za |
13 | 190 | 84.1 | 15.6 | 0.3 |
14 | 201 | 96.9 | 3.1 | 0.03 |
15 | 209 | 99.4 | 0.6 | 0 |
Claims (20)
1. A process for the preparation of 1,1,1,3,3,3-hexafluoropropane, comprising:
(a) contacting at least one halopropane of the formula CF3CH2CHyX3-y, wherein each X is independently selected from the group consisting of F, Cl and Br, and y is 3, 2, or 1, with Cl2 in the liquid phase in the presence of light or a free radical initiator to produce a mixture comprising CF3CH2CClyX3-y;
(b) contacting the CF3CH2CClyX3-y produced in step (a) with HF, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CF3CH2CF3; and
(c) recovering CF3CH2CF3 from the mixture produced in step (b).
2. The process of claim 1 wherein in step (a) the halopropane of the formula CF3CH2CHyX3-y is contacted with Cl2 in the presence of light having a wavelength of from about 250 nm to about 400 nm.
3. The process of claim 2 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from poly(tetrafluoroethylene), and wherein the light is transmitted through the poly(tetrafluoroethylene) portion.
4. The process of claim 2 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from a copolymer of perfluoro(alkyl vinyl ether), and wherein the light is transmitted through the copolymer portion.
5. The process of claim 2 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from a functionalized copolymer of terminally functionalized perfluoro(alkyl vinyl ether), and wherein the light is transmitted through the functionalized copolymer portion.
6. The process of claim 1 wherein in step (b) the contact with HF is carried out in the presence of a fluorination catalyst comprising trivalent chromium.
7. The process of claim 1 wherein the halopropane starting material is photochlorinated at a temperature controlled so that the halopropane starting material and chlorine are primarily in the liquid phase.
8. The process of claim 1 wherein the halopropane starting material is photochlorinated in the presence of a solvent capable of dissolving at least one compound selected from the group consisting of the halopropane starting materials and the step (a) products.
9. The process of claim 8 wherein in step (a) CF3CH2CClF2 is produced from CF3CH2CHF2 starting material.
10. The process of claim 9 wherein in step (b) CF3CH2CClF2 is contacted with HF in the presence of a fluorination catalyst comprising trivalent chromium.
11. The process of claim 7 wherein the halopropane starting material is photochlorinated in a reactor provided with means for keeping halopropane starting materials in the liquid state while permitting HCl released during the chlorination to escape the reactor.
12. The process of claim 11 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from poly(tetrafluoroethylene), and wherein the light is transmitted through the poly(tetrafluoroethylene) portion.
13. The process of claim 12 wherein in step (a) the halopropane of the formula CF3CH2CHyX3-y is contacted with Cl2 in the presence of light having a wavelength of from about 250 nm to about 400 nm.
14. The process of claim 11 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from a copolymer of perfluoro(alkyl vinyl ether), and wherein the light is transmitted through the copolymer portion.
15. The process of claim 14 wherein in step (a) the halopropane of the formula CF3CH2CHyX3-y is contacted with Cl2 in the presence of light having a wavelength of from about 250 nm to about 400 nm.
16. The process of claim 11 wherein step (a) is carried out in a reactor wherein a portion of the reactor wall is fabricated from a functionalized copolymer of terminally functionalized perfluoro(alkyl vinyl ether), and wherein the light is transmitted through the functionalized copolymer portion.
17. The process of claim 16 wherein in step (a) the halopropane of the formula CF3CH2CHyX3-y is contacted with Cl2 in the presence of light having a wavelength of from about 250 nm to about 400 nm.
18. The process of claim 3 wherein the halopropane starting material is photochlorinated in the presence of a solvent capable of dissolving at least one compound selected from the group consisting of the halopropane starting materials and the step (a) products.
19. The process of claim 4 wherein the halopropane starting material is photochlorinated in the presence of a solvent capable of dissolving at least one compound selected from the group consisting of the halopropane starting materials and the step (a) products.
20. The process of claim 5 wherein the halopropane starting material is photochlorinated in the presence of a solvent capable of dissolving at least one compound selected from the group consisting of the halopropane starting materials and the step (a) products.
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PCT/US2005/046264 WO2006069105A1 (en) | 2004-12-22 | 2005-12-19 | Process for the production of 1,1,1,3,3,3-hexafluoropropane |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20080015277A1 (en) * | 2004-12-22 | 2008-01-17 | Velliyur Nott Allikarjuna Rao | Use of Copolymers of Perfluoro(Alkyl Vinyl Ether) for Photochemical Reactions |
US20080149472A1 (en) * | 2004-12-22 | 2008-06-26 | Velliyur Nott Mallikarjuna Rao | Photochlorination and Fluorination Process for Preparation of Fluorine-Containing Hydrocarbons |
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ES2364974T3 (en) * | 2004-12-22 | 2011-09-19 | E.I. Du Pont De Nemours And Company | PHOTOCLORATION AND DEHYDROHALOGENATION PROCEDURE FOR THE PREPARATION OF OLEFINAL COMPOUNDS. |
CN101090767A (en) * | 2004-12-22 | 2007-12-19 | 纳幕尔杜邦公司 | Functionalized copolymers of terminally functionalized perfluoro (alkyl vinyl ether) reactor wall for photochemical reactions, process for increasing fluorine content in hydrocarbons and halohydrocarb |
FR3008093B1 (en) * | 2013-07-04 | 2015-12-11 | Rhodia Operations | PROCESS FOR FLUORINATION OF HALIDE COMPOUNDS OF SULFONYL |
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- 2005-12-19 EP EP05854904A patent/EP1831141A1/en not_active Withdrawn
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US20080015277A1 (en) * | 2004-12-22 | 2008-01-17 | Velliyur Nott Allikarjuna Rao | Use of Copolymers of Perfluoro(Alkyl Vinyl Ether) for Photochemical Reactions |
US20080149472A1 (en) * | 2004-12-22 | 2008-06-26 | Velliyur Nott Mallikarjuna Rao | Photochlorination and Fluorination Process for Preparation of Fluorine-Containing Hydrocarbons |
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